Cyclodextrin-ionic liquid polymer (βCD-BIMOTs-TDI) was firstly synthesized using functionalized β-Cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using toluene diisocyanate (TDI) linker to form insoluble βCD-BIMOTs-TDI. SEM characterization result shows that βCD-BIMOTs-TDI exhibits macropore size while the BET result shows low surface area (1.254 m(2)g(-1)). The unique properties of the ILs allow us to produce materials with different morphologies. The adsorption isotherm and kinetics of 2,4-dichlorophenol (2,4-DCP) onto βCD-BIMOTs-TDI is studied. Freundlich isotherm and pseudo-second order kinetics are found to be the best to represent the data for 2,4-DCP adsorption on the βCD-BIMOTs-TDI. The presence of macropores decreases the mass transfer resistance and increases the adsorption process by reducing the diffusion distance. The change in entropy (ΔS°) and heat of adsorption (ΔH°) for 2,4-DCP on βCD-BIMOTs-TDI were estimated as -55.99 J/Kmol and -18.10 J/mol, respectively. The negative value of Gibbs free energy (ΔG°) indicates that the adsorption process is thermodynamically feasible, spontaneous and chemically controlled. Finally, the interactions between the cavity of βCD-BIMOTs and 2,4-DCP are investigated and the results shows that the inclusion of the complex formation and π-π interaction are the main processes involved in the adsorption process.
β-Cyclodextrin-ionic liquid polymer (CD-ILP) was first synthesized by functionalized β-cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using a toluene diisocyanate (TDI) linker to form insoluble CD-ILP (βCD-BIMOTs-TDI). The βCD-BIMOTs-TDI polymer was characterized using various tools and the results obtained were compared with those derived from the native β-cyclodextrin polymer (βCD-TDI). The SEM result shows that the presence of ionic liquid (IL) increases the pore size, while the thermo gravimetric analysis (TGA) result shows that the presence of IL increases the stability of the polymer. Meanwhile, Brunauer-Emmett-Teller (BET) results show that βCD-BIMOTs-TDI polymer has 1.254 m(2)/g surface areas and the Barret-Joyner-Halenda (BJH) pore size distribution result reveals that the polymer exhibits macropores with a pore size of 77.66 nm. Preliminary sorption experiments were carried out and the βCD-BIMOTs-TDI polymer shows enhanced sorption capacity and high removal towards phenols and As(V).
The removal of four parabens, methyl-, ethyl-, propyl-, and benzyl-paraben, by β-cyclodextrin (β-CD) polymer from aqueous solution was studied. Different β-CD polymers were prepared by using two cross-linkers, i.e., hexamethylene diisocyanate (HMDI) and toluene-2,6-diisocyanate (TDI), with various molar ratios of cross-linker. β-CD-HMDI polymer with molar ratio of 1:7 and β-CD-TDI polymer with ratio 1:4 gave the highest adsorption of parabens among the β-CD-HMDI and β-CD-TDI series, and were subsequently used for further studies. The adsorption capacity of β-CD-HMDI is 0.0305, 0.0376, 0.1854 and 0.3026 mmol/g for methyl-, ethyl-, propyl-, and benzyl-paraben, respectively. β-CD-TDI have higher adsorption capacities compared with β-CD-HMDI, the adsorption capacity are 0.1019, 0.1286, 0.2551, and 0.3699 mmol/g methyl-, ethyl-, propyl-, and benzyl-paraben respectively. The parameters studied were adsorption capacity, water retention, and reusability. Role of both cross-linker in adsorption, hydrophobicity of polymers, and adsorption capacity of different parabens were compared and discussed. All experiments were conducted in batch adsorption technique. These polymers were applied to real samples and showed positive results.
A molecularly imprinted silica gel sorbent for selective removal of 2-Hydroxybenzoic acid (2-HA) was prepared by a surface imprinting technique with a sol-gel process. The 2-HA molecularly imprinted silica gel (2-HA-MISG) sorbent was evaluated by various parameters, including the influence of pH, static, kinetic adsorption and selectivity experiments. The optimum adsorption capacity to the 2-HA appeared to be around pH 2 by the polymer. Morevoer, the imprinted sorbent displayed fast uptake kinetics, obtained within 20 min. The adsorption capacity of the 2-HA-MISG (76.2 mg g-1) was higher than that of the non-imprinted silica gel (NISG) (42.58 mg g-1). This indicates that the 2-HA-MISG offers a higher affinity for 2-HA than the NISG. The polymer displays good selectivity and exhibits good reusability. Experimental results show the potential of molecularly imprinted silica sorbent for selective removal of 2-HA.
Cyclodextrin-ionic liquid polymer (βCD-BIMOTs-TDI) is a new class of macroporous material and has great potential to be used as an SPE adsorbent material for extraction of phenols in river water samples. Six phenols, as model analytes, were extracted on a βCD-BIMOTs-TDI SPE cartridge, and then, eluted with 2 mL of methanol containing 1% acetic acid. The optimum experimental condition was 15 mL of sample volume (sample at pH 6) and 2 mL of methanol containing 1% acetic acid as an eluent solvent. The eluent concentration was determined by using Gas Chromatography-Flame Ionization Detector (GC-FID). Under optimized condition, high sensitivity (detection limits 0.23-0.35 µg/L) and good recoveries (87-116%) were achieved with satisfactory relative standard deviation (RSD) (0.1-1.7%). The developed βCD-BIMOTs-TDI-SPE was then compared with other adsorbents, and the obtained results showed that the βCD-BIMOTs-TDI exhibited higher extraction recovery due to the unique structure and properties. Finally, the βCD-BIMOTs-TDI was applied as a solid phase extraction sorbent for phenols determination under optimized condition, in river and tap waters, prior to the GC-FID separation.
A cloud point extraction (CPE) process using non-ionic surfactant (DC193C) to extract selected paraben compounds from water samples was investigated using reversed phase high performance liquid chromatography (RP-HPLC). The CPE process with the presence of β-cyclodextrin (βCD) functionalized ionic liquid as a modifier (CPE-DC193C-βCD-IL) is a new extraction technique that has been applied on the optimization of parameters, i.e., pH, βCD-IL concentration and phase volume ratio. This CPE-DC193C-βCD-IL method is facilitated at 30 °C, showing great losses of water content in the surfactant-rich phase, resulting in a high pre-concentration factor and high distribution coefficient. The developed method CPE-DC193C-βCD-IL did show enhanced properties compared to the CPE method without the modifier (CPE-DC193C). The developed method of CPE-DC193C-βCD-IL gives an excellent performance on the detection of parabens from water samples with the limit of detection falling in the range of 0.013-0.038 µg mL-1. Finally, the inclusion complex formation, hydrogen bonding, and π-π interaction between the βCD-IL, benzyl paraben (ArP), and DC 193C were proven using 1H NMR and 2D NOESY spectroscopy.
The sequential extraction procedure proposed by the European Standard, Measurements and Testing (SM&T) program, formerly the Community Bureau of Reference (BCR), was applied for partitioning of heavy metals (HMs) in river sediments collected along the course of Sungai Buloh and the Straits of Malacca in Selangor, Malaysia. Eight elements (V, Pb, Cd, Cr, Co, Ni, Cu and Zn) from seven stations (S1-S7) and at different depths were analyzed using the modified BCR Sequential Extraction Procedure (SEP) in combination with ICP-MS to obtain the metal distribution patterns in this region. The results showed that heavy metal contaminations at S2 and S3 was more severe than at other sampling sites, especially for Zn, Cu, Ni and Pb. Nevertheless, the element concentrations from top to bottom layers decreased predominantly. The samples from the Straits of Malacca (S4-S7) the highest contamination factors obtained were for Co, Zn and Pb while the lowest were found for V and Cr, similar to Sungai Buloh sediments. The sediments showed a low risk for V, Cr, Cu and Pb with RAC values of less than 10%, but medium risk for Co, Zn (except S3), Cd at S1 and S2 and Ni at S1, S3 and S5. Zn at S3 and Cd at S3-S7 showed high risk to our sediment samples. There is not any element of very high risk conditions in the selected samples.
In this study, a rapid, specific and sensitive multi-residue method based on acetonitrile extraction followed by dispersive solid-phase extraction (d-SPE) clean-up was implemented and validated for multi-class pesticide residues determination in palm oil for the first time. Liquid-liquid extraction followed by low-temperature precipitation procedure was evaluated in order to study the freezing-out clean-up efficiency to obtain high recovery yield and low co-extract fat residue in the final extract. For clean-up step, d-SPE was carried out using a combination of anhydrous magnesium sulphate (MgSO(4)), primary secondary amine, octadecyl (C(18)) and graphitized carbon black. Recovery study was performed at two concentration levels (10 and 100 ng g(-1)), yielding recovery rates between 74.52% and 97.1% with relative standard deviation values below 10% (n = 6) except diuron. Detection and quantification limits were lower than 5 and 9 ng g(-1), respectively. In addition, soft matrix effects (≤±20%) were observed for most of the studied pesticides except malathion that indicated medium (20-50%) matrix effects. The proposed method was successfully applied to the analysis of suspected palm oil samples.
This study investigated the removal of parabens, N,N-diethyl-m-toluamide (DEET), and phthalates by ozonation. The second-order rate constants for the reaction between selected compounds with ozone at pH 7 were of (2.2 +/-0.2) X 10(6) to (2.9 +/-0.3) X 10(6) M 1/s for parabens, (2.1+/- 0.3) to (3.9 +/-0.5) M-1/s for phthalates, and (5.2 +/-0.3) M-1/s for DEET. The rate constants for the reaction between selected compounds with hydroxyl radical ranged from (2.49 +/-0.06) x 10(9) to (8.5 +/-0.2) x 10(9) M-1/s. Ozonation of selected compounds in secondary wastewater and surface waters revealed that ozone dose of 1 and 3 mg/L yielded greater than 99% depletion of parabens and greater than 92% DEET and phthalates, respectively. In addition, parabens were found to transform almost exclusively through the reaction with ozone, while DEET and phthalates were transformed almost entirely by hydroxyl radicals (.OH).
This study investigated the reaction kinetics and degradation mechanism of parabens (methylparaben, ethylparaben, propylparaben and butylparaben) during ozonation. Experiments were performed at pH 2, 6 and 12 to determine the rate constants for the reaction of protonated, undissociated and dissociated paraben with ozone. The rate constants for the reaction of ozone with dissociated parabens (3.3 × 10(9)-4.2 × 10(9)M(-1)s(-1)) were found to be 10(4) times higher than the undissociated parabens (2.5 × 10(5)-4.4 × 10(5)M(-1)s(-1)) and 10(7) times higher than with the protonated parabens (1.02 × 10(2)-1.38 × 10(2)M(-1)s(-1)). The second-order rate constants for the reaction between parabens with hydroxyl radicals were found to vary from 6.8 × 10(9) to 9.2 × 10(9)M(-1)s(-1). Characterization of degradation by-products (DBPs) formed during the ozonation of each selected parabens has been carried out using GCMS after silylation. Twenty DBPs formed during ozonation of selected parabens have been identified. Hydroxylation has been found to be the major reaction for the formation of the identified DBPs. Through the hydroxylation reaction, a variety of hydroxylated parabens was formed.
A simple and effective multiresidue method based on precipitation at low temperature followed by matrix solid-phase dispersion-sonication was developed and validated to determine dimethoate, malathion, carbaryl, simazine, terbuthylazine, atrazine and diuron in palm oil using liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS). Liquid-liquid extraction (LLE) followed by low temperature method were optimized by studying the effect of type and volume of organic solvent (acetonitrile, acetonitrile:n-hexane (3:2 v/v) and acetone) and time of freezing to obtain high recovery yield and low co-extract fat residue in the final extract. The optimal conditions for matrix solid-phase dispersion (MSPD) were obtained using 5 g of palm oil, 2 g of primary secondary amine (PSA) as dispersing sorbent, 1 g of graphitized carbon black (GCB) as clean-up sorbent and 15 mL of acetonitrile as eluting solvent under conditions of 15 min ultrasonication at room temperature. Method validation was performed in order to study sensitivity, linearity, precision, and accuracy. Average recoveries at three concentration levels (25, 50 and 100 μg kg(-1)) were found in the range of 72.6-91.3% with relative standard deviations between 5.3% and 14.2%. Detection and quantification limits ranged from 1.5 to 5 μg kg(-1) and from 2.5 to 9 μg kg(-1), respectively.
This study was undertaken in order to understand the factors affecting the degradation of an insect repellent, N,N-diethyl-m-toluamide (DEET) by ozonation. Kinetic studies on DEET degradation were carried out under different operating conditions, such as varied ozone doses, pH values of solution, initial concentrations of DEET, and solution temperatures. The degradation of DEET by ozonation follows the pseudo-first-order kinetic model. The rate of DEET degradation increased exponentially with temperature in the range studied (20-50 degrees C) and in proportion with the dosage of ozone applied. The ozonation of DEET under different pH conditions in the presence of phosphate buffer occurred in two stages. During the first stage, the rate constant, k(obs), increased with increasing pH, whereas in the second stage, the rate constant, k(obs2), increased from pH 2.3 up to 9.9, however, it decreased when the pH value exceeded 9.9. In the case where buffers were not employed, the k(obs) were found to increase exponentially with pH from 2.5 to 9.2 and the ozonation was observed to occur in one stage. The rate of degradation decreased exponentially with the initial concentration of DEET. GC/MS analysis of the by-products from DEET degradation were identified to be N,N-diethyl-formamide, N,N-diethyl-4-methylpent-2-enamide, 4-methylhex-2-enedioic acid, N-ethyl-m-toluamide, N,N-diethyl-o-toluamide, N-acetyl-N-ethyl-m-toluamide, N-acetyl-N-ethyl-m-toluamide 2-(diethylamino)-1-m-tolylethanone and 2-(diethylcarbamoyl)-4-methylhex-2-enedioic acid. These by-products resulted from ozonation of the aliphatic chain as well as the aromatic ring of DEET during the degradation process.
A flow injection (FI) method with on-line preconcentration using a mini-column loaded with 8-hydroxyquinoline immobilized on controlled pore glass (CPG-8HQ) is described for the determination of trace metals by ion chromatography (IC) with pyridine-2-6-dicarboxylic acid (PDCA) as the eluent. Copper, cadmium, lead, zinc, nickel and iron were determined at ppb level after post-column derivatization with 4-(2-pyridylazo)-resorcinol (PAR). The detection limits (3sigma) for the FI/IC system were 8.27, 0.89, 0.09, 0.06, 0.09 and 0.07 g l(-1) for Pb(2+), Cd(2+), Cu(2+) Ni(2+), Zn(2+) and Fe(3+), respectively, using 5 ml sample volume. The method was applied to the analysis of Malaysian natural waters.
The reactions of 2-chloropyrimidine with methylamine, ethylamine and piperidine gave the corresponding 2-N-methylamino-, 2-N-ethylamino- and 2N- piperidinopyrimidines, respectively. The fluorescence properties of these alkylamino derivatives in chloroform, ethyl acetate, carbon tetrachloride, acetone, ether, ethanol and methanol were studied. All the alkylamino derivatives showed the highest fluorescence intensity in polar protic solvents; thus 2-N-methylaminopyrimidine (highest fluorescence intensity at 377 nm when excited at 282 nm) and 2-N-ethylaminopyrimidine (highest fluorescence intensity at 375 nm, when excited at 286 nm) showed the highest fluorescence in methanol. In ethanol, 2-N-piperidinopyrimidine showed a fluorescence peak at 403 nm when excited at 360 nm and in chloroform it fluoresced at 392 nm when excited at 356 nm.
PM10 airborne particles and soot deposit collected after a fire incident at a chemical store were analyzed in order to determine the concentrations of polycyclic aromatic hydrocarbons (PAHs). The samples were extracted with 1:1 hexane-dichloromethane by ultrasonic agitation. The extracts were then subjected to gas chromatography-mass spectrometric (GC-MS) analysis. The total PAHs concentrations in airborne particles and soot deposit were found to be 3.27 +/- 1.55 ng/m3 and 12.81 +/- 24.37 microg/g, respectively. Based on the molecular distributions of PAHs and the interpretation of their diagnostic ratios such as PHEN/(PHEN + ANTH), FLT/(FLT + PYR) and BeP/(BeP + BaP), PAHs in both airborne particles and soot deposit may be inferred to be from the same source. The difference in the value of IP/(IP + BgP) for these samples indicated that benzo[g, h, i] perylene and coronene tend to be attached to finer particles and reside in the air for longer periods. Comparison between the molecular distributions of PAHs and their diagnostic ratios observed in the current study with those reported for urban atmospheric and roadside soil particles revealed that they are of different sources.
The growth response, metal tolerance and phytoaccumulation properties of water spinach (Ipomoea aquatica) and okra (Abelmoschus esculentus) were assessed under different contaminated spiked metals: control, 50 mg Pb/kg soil, 50 mg Zn/kg soil and 50 mg Cu/kg soil. The availability of Pb, Zn and Cu metals in both soil and plants were detected using flame atomic absorption spectrometry. The concentration and accumulation of heavy metals from soil to roots and shoots (edible parts) were evaluated in terms of translocation factor, accumulation factor and tolerance index. Okra recorded the highest accumulation of Pb (80.20 mg/kg) in its root followed by Zn in roots (35.70 mg/kg) and shoots (34.80 mg/kg) of water spinach, respectively. Different accumulation trends were observed with, Pb > Zn > Cu in okra and Zn > Pb > Cu in water spinach. Significant differences (p
The occurrence of n-alkanoic acids, amides, and nitriles in samples of aerosol particulate matter from Kuala Lumpur and Santiago suggests that emissions from cooking and biomass burning are the primary sources of these organic markers in the atmosphere. It is proposed that fatty acids react with ammonia during biomass burning or combustion to produce amides and nitriles, which can be applied as useful biomarker tracers. To test this hypothesis, nonadecanoic acid and hexadecanamide were used as reactants in hydrous pyrolysis experiments. These experiments produced amides and nitriles and indicated that ammonia is an essential agent in their formation. Thus amides and nitriles are of utility as indicators for input from combustion and biomass burning in the ambient atmosphere.
Three different types of low cost soil amendments, namely, EDTA, elemental S and N-fertilizer, were investigated with Vetiver grass, Vetiveria zizanioides (Linn.) Nash growing under highly mixed Cd-Pb contamination conditions. A significant increase (p
This study investigated the degradation pathway of metoprolol, a widely used β-blocker, in the ozonation via the identification of generated ozonation by-products (OPs). Structure elucidation of OPs was performed using HPLC coupled with quadrupole time-of-flight high-resolution mass spectrometry. Seven OPs were identified, and four of these have not been reported elsewhere. Identified OPs of metoprolol included aromatic ring breakdown by-products; aliphatic chain degraded by-products and aromatic ring mono-, di-, and tetrahydroxylated derivatives. Based on the detected OPs, metoprolol could be degraded through aromatic ring opening reaction via reaction with ozone (O3) and degradation of aliphatic chain and aromatic ring via reaction with hydroxyl radical (•OH).
The trace metal concentrations in edible muscle of red tilapia (Oreochromis spp.) sampled from a former tin mining pool, concrete tank and earthen pond in Jelebu were analysed with microwave assisted digestion-inductively coupled plasma-mass spectrometry. Results were compared with established legal limits and the daily ingestion exposures simulated using the Monte Carlo algorithm for potential health risks. Among the metals investigated, arsenic was found to be the key contaminant, which may have arisen from the use of formulated feeding pellets. Although the risks of toxicity associated with consumption of red tilapia from the sites investigated were found to be within the tolerable range, the preliminary probabilistic estimation of As cancer risk shows that the 95th percentile risk level surpassed the benchmark level of 10(-5). In general, the probabilistic health risks associated with ingestion of red tilapia can be ranked as follows: former tin mining pool > concrete tank > earthen pond.